Certain polyepoxide-modified oxyalkylation derivatives being obtained in turn by oxyalkylation of certain polyols having at least three hydroxyls



United States Patent 2,996,551 CERTAIN POLYEPOXIDE-MODIFIED OXYALKYL- ATION DERIVATIVES BEING OBTAINED IN TURN BY OXYALKYLATION OF CERTAIN POLYOLS HAVING AT LEAST THREE HYDROX- Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware N0 Drawing. Original application Sept. 24, 1953, Ser. No. 382,201. Divided and this application Dec. 6,1956, Ser. No. 626,613

2Claims. (Cl. 260-615) This application is a division of our copending application Serial No. 382,201, filed September 24, 1953, and now Patent No. 2,792,354.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification. Particularly, the invention is concerned with the preparation of certain high molal oxyalkylation derivatives, and particularly oxypropylation derivatives, of certain monomeric polyhydric compounds, hereinafter described in detail, and certain non-aryl hydrophile polyepoxides, also hereinafter described in detail.

In essence, the production of the compounds involves the preparation of oxyalkylated derivatives, and then re acting the same with the polyepoxide, particularly the diepoxide.

As to the preparation of the oxyalkylated derivatives and particularly oxypropylated derivatives, see U.S. Patents Nos. 2,552,528, dated May 15, 1951, 2,552,529, dated May 15, 1951, 2,605,232, dated July 29, 1952, and 2,626,910, dated January 27, 1953, all to Melvin De Groote.

Water-soluble polyhydric materials may be subjected to oxyalkylation in the manner described in the four patents, preceding, and particularly oxypropylation. However, if desired, they may be oxyalkylated by use of an alkylene carbonate, such as ethylene carbonate, propylene carbonate or butylene carbonate; or, what is more feasible, from a practical standpoint, is to initially oxyalkylate by means of an alkylene carbonate and then employ an alkylene oxide, particularly propylene oxide. Such procedure employed in connection with compounds of the kind herein employed as raw materials is described in co-pending applications, Serial'Nos. 359,661 through and including 359,669, all dated June 4, 1953, to Monson and Dickson of which Serial Nos. 359,666; 359,667; and 359,669 are now abandoned. Application Serial No. 359,661 is now Patent No. 2,819,261; application Serial No. 359,662 is now Patent No. 2,819,260; application Serial No. 359,663 is now Patent No. 2,854,447; application Serial No. 359,664 is now Patent No. 2,854,449; application Serial No. 359,665 is now Patent No. 2,766,- 292 and application Serial No. 359,668 is now Patent No. 2,854,444.

Reference is made to U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this test with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the water-in-oil type is characterized by the fact that a 50-50 solution in xylene,

ice

or its equivalent, when mixed with one to three volumes of water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be divided into six parts:

Part 1 is concerned with the hydrophile non-aryl poly-- epoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with suitable polyols which are reacted with monoepoxides;

Part 3 is concerned with suitable monoepoxides and the oxyalkylation of the polyols by means of said epoxides;

Part 4 is concerned with reactions involving the two previously described types of materials, i.e., the oxyalkylated polyols on the one hand and polyepoxides, and particularly diepoxides, on the other hand;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products and Part 6 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the non-aryl polyepoxides and partic ularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U.S. Patent No. 2,070,990, dated February 16, 1937, to Groll et al.;-and U.S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

H H H H HC CC/CH CH3 H l H H HO-/G-C\-/OH In some instances the compounds are essentially derivatives of etherized epichlo-rohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U.S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula:

The diepoxides previously described may be indicated by the following formula:

As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is 1. In another example previously referred to R" is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof, in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be water-soluble in substantially all proportions, i.e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by H H H -CCOH Thus, R(OH) where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived, or theoretically derived at least, from water-insoluble diols or water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula H H H H H H CCCO[R1]OCCCH in which R is C H (OH), it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields 4 triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl other is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams in stead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds, is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the S-membered ring, followed by conversion of the terminal bydroxyl groups into epoxy radicals.

See Canadian Patent No. 672,935.

PART 2 As to suitable polyols reference is made to the description of water-soluble polyols having at least 4 hydroxyls as appears in U.S. Patent No. 2,552,528, dated May 15, 1951, to De Groote. Subsequent description will appear in regard to polyols having 3 hydroxyl groups. Said description is found in said patent beginning with column 2, line 39, through and including column 15, line 37.

As has been pointed out previously, for the purpose of the present invention the polyols need not have 4 hydroxyl radicals but may have as many as 3. 'Ihe most common trihydric polyol is glycerol. Other suitable trihydric polyols include trimethylolethane. Additional trihydric polyols may be obtained from monohydric alcohols by reaction with 2 moles of glycide or methylglycide. Similarly, they may be obtained from dihydric alcohols, i.e., diols such as ethylene, propylene or butylene glycol by reaction with one mole of glycide or methylglycide. Polyols can be obtained from polyhydric alcohols having 4 hydroxyls by an etherization step so as to eliminate one hydroxyl radical. For instance, acyclic diglycerol can be reacted with a methylating agent so as to produce the monomethyl ether. Likewise, sorbitan can be treated in a similar manner.

In regard to suitable ethers also having more than 3 hydroxyl radicals, reference is made to methylglucoside which is available in the open market.

More specifically, as to suitable examples, particularly those having 4 or more hydroxyl groups, reference is made to U.S. Patent No. 2,450,079, dated September 28, 1948, to Brown, which, in turn, is referred to in aforementioned U.S. Patent No. 2,552,528. Said U.S. patent in defining a polyol which is perfectly acceptable for the instant purpose, states as follows:

Polyols which may be used are those of relatively low carbon content which contain at least 3 hydroxyl groups. By the term polyols, as used in this specification, are meant polyhydric alcohols and carbohydrates. Since the use of polyols of high carbon content per molecule tends to result in end products which are not sufficiently waxy and plastic, it is preferred to use polyols having not more than 12 carbon atoms per molecule. As exemplary of polyols which may be employed may be listed glycerol and the higher polyhydric alcohols, the cyclitols such as inositols, and partially alkylated cyclitols such as quebrachitol and pinitol, diglycerol and the lower polyglycerols, pentaerythritol, di-pentaerythritol and other pentaerythritol ethers, hexitane, such as sorbitan and mannitan, saccharides such as glucose, fructose, lower alkyl glucosides, sucrose, lactose, trehalose, glucosan, and mannosan, and lactones such as gluconiclactone. Polyols containing up to 6 carbon atoms in particular have yielded valuable products. Examples of such are glycerol, mannitan, hexitols, such as sorbitol, mannitol, commercial sorbitol syrup, and hexoses, such as glucose. Mixture of polyols, such as partially reduced sugars, also may be employed.

PART 3 The nonhydroxylated monoepoxides employed for reaction with the polyols are monoepoxides free from a hydroxyl radical and having not over 4 carbon atoms, to wit, ethylene oxide, propylene oxide, and butylene oxide. Since the purpose is to obtain a water-insoluble product in the initial stage as well as a product which is xylenesoluble, it is obvious the amount of ethylene oxide which can be used is comparatively small. It may be used, for example, to convert a polyol which is not too water-soluble, such as dipentaerythritol, into a more water-soluble form. The oxide which is most satisfactory, both from the standpoint of reactivity and cost is propylene oxide. Butylene oxide, or rather any of the butylene oxide is almost twice the cost of propylene oxide it is obvious there is no advantage in using butylene oxide except in special circumstances and perhaps to permit the incidental use of a greater amount of ethylene oxide. For instance subsequent reference is made to products as described in the four aforementioned U.S. Patents Nos. 2,552,528, 2,552,529, 2,605,232 and 2,626,910.

The solubility eifect introduced by oxybutylation depends in part whether it is the 1,2 oxide or the 2,3 oxide. In most cases 4 moles of butylene oxide can be replaced by one mole of ethylene oxide and 3 moles of butylene oxide. In some circumstances 3 of propylene oxide may be replaced, by two moles of butylene oxide and one of ethylene oxide. If desired, one could use a mixture of propylene oxide and ethylene oxide in which the ethylene oxide represented just a few percent by weight. Mixtures of butylene oxide and propylene oxide can be used either alone or in conjunction with ethylene oxide. How over, for sake of brevity it is believed the subsequent text can be limited to oxypropylation for reasons pointed out and because the variants above indicated are obvious.

As to the production of oxypropylated derivatives, reference is made to Part 2 of U.S. Patent No. 2,552,-

528 beginning at column 15, line 39, and ending at column 21, line 72; also to Part 2 of U.S. Patent 2,552,- 529 beginning at column 13, line 27 and ending at column 21, line 46; to U.S. Patent No. 2,605,232, column 4, Part 4, line 51, and ending at column 11, line 37; and to U.S. Patent No. 2,626,910, Part 1, colurrm 2, line 2, and ending at column 8, line 42.

The objection to the use of hydroxylated monoepoxides, such as glycide or methylglycide, is primarily the cost and, secondly, the fact that they introduce water-soluble characteristics comparable to ethylene oxide. This does not mean that if desired one could not introduce the use of glycide or methylglycide in the procedure which involves reaction with a monoepoxide or at the end of the procedure. In fact, in some instances it is desired to use one or more moles of glycide at some stage per initial hydroxyl group in order to give a branch chain during subsequent reaction with butylene oxide or the like. It is obvious, also, that if desired one could introduce the use of a glycol ether, such as glycidylisopropyl ether, glycidylphenyl ether, etc. Such variants except giving a branched chain eflfect, add little or nothing to the general structure and require no further elaboration.

PART 4 if the oxyalkylated polyol is designated as (A) and the diglycidyl ether as (B), the resultant larger molecule may be indicated as (ABA). If another mole of the diglycidyl ether is employed then these two larger molecules could be tied together so as to give a molecule approximately 4 times the size of the initial molecule which could be indicated as (ABABABA). It is evident this would just be a continuation by further use of the reactant and all that is necessary is to avoid cross-linking, gelation or formation of an insoluble material. This generally presents no difiiculty and if such difficulty arises it can be avoided by use of a larger amount of solvent, or by the use of a lower temperature of reaction, or by use of an oxyalkylated polyol having a longer chain length between hydroxyl groups.

For reasons of brevity what is said hereinafter will be concerned largely with the reaction involving 2 moles of the oxyalkylated polyol and one mole of the diglycidyl ether, as specified. The reaction is essentially an oxyalkylation reaction and thus may be considered as merely a continuance of the previous oxyalkylation reaction. The previous oxyalkylation reaction involved a monoepoxide as differentiated from a polyepoxide and particularly a diepoxide. The reactions take place in substantially the same Way, i.e., by the opportunity to react at somewhere above the boiling point of water and below the point of decomposition, for example, -185 C. in the presence of a small amount of alkaline catalyst. Since the polyepoxide is non-volatile as compared, for example, with ethylene oxide, the reaction is comparatively simple. Purely from a mechanical standpoint it is a matter of convenience to conduct both classes of reactions in the same equipment. In other words, after the polyol has been reacted with propylene oxide or the like, it is subsequently reacted with a polyepoxide. The polyepoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U.S. Patent No. 2,499,365. One can use a variety of catalysts in connection with the polyepoxide of the same class eml ployed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. The usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other cataation involving the initial stage and permitting the solvent to remain. The amount of solvent may be insig nificant, depending whether or not exhaustive oxyalkylation is employed. However, since the oxyalkylated polylysts may be acidic in nature and are of the kind charac- 01s are almost invariably liquids there is no need for the terized by iron and tin chlorides. Furthermore, insoluble presenceof a solvent as when oxyalkylation involves 2 catalysts such as clays or specially prepared mineral sohd which may be rather high melting. Thus, it is 1mcatalysts have been used. For practical purposes, it is rnater lal Whether there 15 a solvent present or not and best to use the same catalyst as is used in the initial oxy- 1t 18 lmmaterlal Whether solvent was added n the first alkylation step and in many cases there is sufiicient resid- Stage f oxyalkylatlon and also 1t 18 lmmaterlal ual catalyst to serve for the reaction involving the second Whether there was Solvent Present in Second Stage of oxyalkylation step, i.e., the polyepoxide. For this reayalkylatlon r n t. The advantage of the presence of Son, We have preferred to use a ll amount f finely solvent 1s that sometimes it 1s a convement way of condivided caustic soda or sodium methylate as the initial tfolllllg the reactloh temperature t thus 111 the Subsecatalyst and also the catalyst in the second stage. The qlleht 8 1112138 We have added sufficient xyl n as t amount generally employed is 1%, 2%, or 3%, f th produce a mixture which boils somewhere 1n the neighboralkaline catalysts hood of 125 C. to 140 C. and removes xylene so as to Actually, the reactions of polyepoxides with various brlrfg the bolllhg Polllt t the mlXtufe about resins have been thoroughly described in the literature durmg P of the Teactlol} and Subsequently famovlhg and the procedure is, for all practical purposes, the same 20 more xyleneoso that mlxture l'efluxed at Somewhfife as with glycide which has been described in one or more Petween 170 to 190 Thls was P F Y a convenof the previously mentioned U.S. Patents Nos. 2,552,528, lence and need not be employed unless deslred- 2,552,529, 2,605,232 and 2,6216,9O. Sf course}; in th; Example A1 instant process one is not invo ve wit a resin ut w1t an oxyalkylated polyol but the reactions are essentially g s gg f g P iy g s g the same since the point of reactivity is a labile hydrogen 2 552 5 p e m a oremen a an atom. 28. The oxyalkylated derlvatrve had a molecular It goes without saying that the reaction involving the g ggi g g ga gg g? g t z i g polyepoxide can be conducted in the same manner as the g: 0X r0 i i eluaer gis t}? g monoepoxide as far as the presence of an inert solvent h g ori f 1 i f 61' 0 is concerned, i.e., one that is not oxyalkylation-suscepty ams of g g fi ible. Generally speaking, this is most conveniently an ed i a zg a a 6 5 were aromatic solvent such as xylene or a higher boiling coal exactl gg q z f 3. tar solvent, or else a similar high boiling aromatic solg cm pow are mm methylate was added to equal 1.5 grams. The mlxture vent obtained from petroleum. One can employ an oxyo was stirred and the temperature rose to 150 C. and 18.5 genated solvent, such as the dlethylether of ethylene mm of die oxide A reviousl described Wet add d glycol, or the diethylether of propylene glycol, or similar gr 1 f y e e thers either alone or in combination with a hydrocarbon over approxlmate y mmute ppnod' The mlxture e 1 Th 1 1 d h M b h was allowed to react for a total period of about 3 hours so vent. e so vent so se ecte s 011 e one W 16 40 at the maximum temperature or slightly below. At the of course, is suitable in the oxyalkylatlon step involving end of this time the reaction was stopped and the Prod the monoepoxides described subsequently. The solvent uet represented a dark Viseeus mass Selected y depend on the ablhty t0 Ifimove It y For reasons pointed out description of further exsequent distillation if required. Here again it has been amples will be limited to a tabular presentation which our preference to have a solvent present in the oxyalkylappears in following Tables I, II, III and IV.

TABLE I No. of Ex. O.S.C.1 of U.S. M01. Amount Polyol from which 080 Hydrox- No is Ex Patent Wt. Used, is Derived yls in No. No. (Theo.) Grams Original Polyol AL... 2 2, 552. 528 1,296 129.6 Peutaerythritol 4 52.--. 3 2,552,528 1. 414 141.4 Dipentaerythritol 6 A3.--. 4 2,552,528 1,532 153.2 Tri-pentaerythritol 8 A4---. 28 2,552,528 4,850 485.0 Monoglycerol ether of 5 pentaerythritol. A5.-.. 29 2, 552, 528 4, 968 496.8 Mouoglycerol ether of di- 7 peutaerythritol. A6 30 2, 552, 528 5, 088 508.8 Monoglycerol ether of tri- 9 entaerythritol. A7---- 54 2,552,528 7,140 714.0 Monoethyleneglycolether 4 of pentaerythritol. A8.... I 2,552,529 1,464 146.4 Sorbitol 6 .49.--- M 2,552,529 3,500 350.0 .do 6 A 5 2, 552, 529 1,416 141.6 Monigglylcerol ether of 7 S01 1 0 A11-.- 10 2,552,529 1,490 149.0 Digltyeerol ether of mans 111 O A12-.- 13 2,552,529 1,606 160.6 Hexaethyleneglycol ether 6 of sorbitol. A13--- 47 2,552,529 10,056 100.6 Momg lylcerol ether of 7 O l O A14-.- 52 2,552,529 10,130 101.3 Digliyeerol ether of man- 8 I1 0 A15.-- 55 2,552,529 10, 246 102.5 Hexaethyleueglycol ether 6 of sorbitol. A16... 22 2,626,910 3,110 311.0 Dextrose 5 A17... 42 2,626,910 6,320 .--..do 5 A18... 42 2, 505, 232 4, 485 4 A19... 82 505,232 10,900 4 A20... 911 2, 505, 232 1, 77s 4 1 0.8.0. means oxyalkylation-susceptible compound.

TABLE 11 Diepox- Catalyst Time Max. Color and Ex. ide Amt, (N 20 CH3), Xylene, Molar of Reac- Temp., Physical No. Used gms. gms. gms. Ratio tfign, 0. State A 18. 5 1. 5 148 2:1 3 150 Dark viscous mass. A 18. 5 1. 6 160 2:1 3 154 DO. A 18. 5 1. 7 172 2: 1 3 165 0. A 18. 5 5.0 504 2: 1 3 158 DO. A 18.5 5.1 515 2:1 3 160 DO A 18. 5 5. 2 527 2: 1 3 166 Do. A 18. 5 7. 3 733 2: 1 3 165 DO. A 18.6 1.6 165 2: 1 3 158 Do. A 18. 5 3. 7 169 2: 1 3 160 Do. A 18.5 1. 6 160 2:1 3 160 A 18. 1. 6 168 2:1 3 148 Do. A 18. 5 1. 8 179 2:1 3 156 Do. A 1. 9 1. 2 103 2:1 3 160 DO. A 1.9 1.2 103 2:1 3 155 DO A 1. 9 1. 2 104 2: 1 3 158 DO. A 18.5 3. 3 330 2: 1 3 155 DO. A 18.5 6. 5 650 2: 1 3 164 Do A 18.5 4. 6 467 2: 1 3 160 Do. A 1. 9 1. 2 111 2: 1 3 162 Do A 18. 5 1. 9 196 2:1 3 160 D0.

TABLE III No. 0 1 Ex. 0.8.0. of U.S. M01. Amount Polyol from which 050 Hydrox- No. is Ex. Patent Wt. Used, is Derived yls in N o. No. (Theo.) Grams Original Polyol B1- 2 2, 552, 528 1, 296 129. 6 Pentaerythritol 4 B2 3 2, 552, 528 1, 414 141. 4 Di-pentaerythritoL- 6 183-... 4 528 1, 532 153. 2 Tri-pentaerythritol 8 134--.. 28 2, 552, 528 4, 850 485. O Monoglycerol ether of pen- 5 taerythritol.

185-... 29 2, 552, 528 4, 968 496.8 Monoglycerol ether of di- 7 pentaerythritol.

136--.. 30 2, 552, 528 5, 088 508. 8 Monoglycerol ether of tri- 9 pentaerythritol.

B7 54 2, 552, 528 7, 140 714.0 Monoethyienegiycol ether 4 of pentaerythrl 13s---. I 2, 552, 529 1, 464 146. 4 Sorbitol 6 139.-.. M 2, 552, 529 a, 500 350. 0 ..do 6

B 5 2, 552, 529 1, 416 141. 6 Mgitogilycerol ether of sor- 7 1 o B11--. 2, 552, 529 1, 490 149. 0 Dig 1ycero1ether of man- 8 B12.-. 13 2, 552, 529 1, 606 160. 6 Hexaethyleneglycol ether 6 of sorbitol.

B13.-. 47 2, 552, 529 10, 056 100.6 Mgfiog lycerol ether of sor- 7 1 o B14--. 52 2, 552, 529 10, 130 101. 3 Dig lycerol ether of man- 8 B15--. 2, 552, 529 10, 246 102.5 Hexaethyieneg1yco1 ether 6 of sorbitol.

B16... 22 2, 626, 910 3, 311. 0 Dextrose 5 TABLE IV Diepox- Catalyst Time Max. Color and Ex. ide Amt, (N aOCHa), Xylene, Molar of Reac- Temp., Physical No. Used gms. gms. gms. Ratio tfign, 0. State BL--- B 11 1 4 141 2.1 3 160 Dark Viscous mass.

B 11 1. 5 152 2:1 3 155 Do B 11 1. 6 164 2:1 3 D0. B 11 5. 0 496 2:1 3 152 D0. B 11 5. 1 507 2:1 3 158 D0. B 11 5. 2 520 2:1 3 154 D0 B 11 7. 3 725 2:1 3 154 Do B 11 1. 6 157 2:1 3 D0. B 11 3. 6 361 2'1 3 150 0. B 11 1. 5 153 2: 1 3 153 D0. B 11 1. 6 160 2: l 3 153 D0. B 11 1. 7 172 2:1 3 150 D0. B 1. 1 1. 0 102 2: 1 3 148 D0. B 1.1 1.0 102 2:1 3 150 D0. B 1. 1 1.0 104 2:1 3 150 D0. B 11 3. 2 322 2:1 3 149 D0. B 11 6. 4 643 2: 1 3 150 D0. B 11 4. 6 460 2:1 3 152 Do. B 1.1 1. 1 110 2:1 3 150 0. B 11 1. 9 189 2:1 3 150 D0.

11 PART As to the use of conventional demulsifying agents reference is made to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example A7, herein described.

PART 6 The products, compounds, or the like herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-inoil type as described in detail in Part 5 immediately preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cationactive materials. Instead of an imine, one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure I HaCN wherein R and R" are alkyl groups.

It is not necessary to point out that after reaction with a reactant of the kind described which introduce a basic nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 5, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 4, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes; as ingredients in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may be used also for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these doubly oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The doubly oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial polyol, the particular monoepoxide selected, and the ratio of monoepoxide to polyol, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type; as additives in the flotation of ores, and at times as aids in 12 chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system for two otherwise insoluble phases.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. The product resulting from manufacturing process of reacting under oxyalkylation conditions (A) high molal oxypropylation derivatives of monomeric polyhydric compounds tion end-product in respect to water and xylene being I substantially the result of the oxypropylation step;

(g) the ratio of propylene oxide per hydroxyl in the initial polyhydric reactant being within the range of 7 to 70;

(h) the initial polyhydric reactant representing up to 12 /z% by weight of the oxypropylation end-product on a statistical basis;

(i) the preceding being based on complete reaction involving the propylene oxide and the initial polyhydric reactant; and

\ (B) a non-aryl hydrophile diepoxide containing two terminal 1,2-epoxy rings obtained by replacement of two oxygen linked hydrogen .atoms in a water-soluble polyhydric alcohol by the radical n H H C-C CH H the ratio of reactant (A) to reactant (B) being in the proportion-of 2 moles of (A) to one mole of (B); said reactive compounds (A) and (B) being members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; the reaction product being .a member of the class of liquids and solvent-soluble solids; said reactionfbetween (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The product of claim 1 in which the non-aryl polyepoxide is a hydroxylated diepoxy polyglycerol having not over 20 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 2,503,726 Greenlee Apr. 11, 1950 2,552,528 De Groote May 15, 1951 2,552,529 De Groote May 15, 1951 

1. THE PRODUCT RESULTING FROM MANUFACTURING PROCESS OF REACTING UNDER OXYALKYLATION CONDITIONS (A) HIGH MOLAL OXYPROPYLATION DERIVATIVES OF MONOMERIC POLYHYDRIC COMPOUNDS (A) THE INITIAL POLYHYDRIC REACTANT HAVING 4 TO 9 HYDROXYL RADICALS AND BEING SELECTED FROM THE GROUP CONSISTING OF POLYGLYCEROLS, PENTAERYTHRITOLS, SUGARS, SUGAR ALCOHOLS AND THEIR ETHYLENE GLYCOL, POLYETHYLENE GLYCOL, GLYCEROL AND POLYGLYCEROL ETHERS, (B) THE INITIAL POLYHYDRIC REACTANT HAVING A MOLECULAR WEIGHT OF ABOUT 136 TO ABOUT 455 (C) THE INITIAL POLYHYDRIC REACTANT BEING WATER-SOLUBLE AND XYLENE-INSOLUBLE, (D) THE OXYPROPYLATION END-PRODUCT BEING WATER-INSOLUBLE AND XYLENE-SOLUBLE, (E) THE OXYPROPYLATION END-PRODUCT BEING WITHIN THE MOLECULAR WEIGHT RANGE OF 1300 TO 10,000 ON AN AVERAGE STATISTICAL BASIS, (F) THE SOLUBILITY CHARACTERISTICS OF THE OXYPROPYLATION END-PRODUCT IN RESPECT TO WATER AND XYLENE BEING SUBSTANTIALLY THE RESULT OF THE OXYPROPYLATION STEP, (G) THE RATIO OF PROPYLENE OXIDE PER HYDROXYL IN THE INITIAL POLYHYDRIC REACTANT BEING WITHIN THE RANGE OF 7 TO 70, (H) THE INITIAL POLYHYDRIC REACTANT REPRESENTING UP TO 12 1/2% BY WEIGHT OF THE OXYPROPYLATION END-PRODUCT ON A STATISTICAL BASIS, (I) THE PRECEDING BEING BASED ON COMPLETE REACTION INVOLVING THE PROPYLENE OXIDE AND THE INITIAL POLYHYDRIC REACTANT, AND (B) A NON-ARYL HYDROPHILE DIEPOXIDE CONTAINING TWO TERMINAL 1,2-EPOXY RINGS OBTAINED BY REPLACEMENT OF TWO OXYGEN LINKED HYDROGEN ATOMS IN A WATER-SOLUBLE POLYHYDRIC ALCOHOL BY THE RADICAL 